Method of manufacturing heavy water



Sept. 27, 1960 P. HARTECK 2,954,279

METHOD OF MANUFACTURING HEAVY WATER Filed Feb. 23. 1954 4 Sheets-Sheet 1 byM M ATTORNEYS Sept. 27, 1960 P. HARTECK 2,954,279

METHOD OF MANUFACTURING HEAW WATER Filed Feb. 23, 1954 4 Sheets-Sheet 2 //v VEN TOR Pau/ fiar/eck Arron/v5 Y5 Sept. 27, 1960 P. HARTECK 2,

METHOD OF MANUFACTURING HEAVY WATER Filed Feb. 23, 1954 4 Sheets-Sheet 3 //v VEN TOR P0 41/ Har/eck AT ORNE Y5 Sept. 27, 1960 'P. HARTECK 2,954,279.

I METHOD OF MANUFACTURING HEAVY WATER Filed Feb. 25, 1954 Y 4 Sheets-Sheet 4 VEN TOR Pau/ HdF/ECk A'TTORNE Y5 2,954,279 Patented Sept. 27, 1960 METHDD OF MANUFACTURING HEAVY WATER Paul Harteck, Troy, N.Y., assignor to Rensselaer Polytechnic Institute, Troy, N.Y., a corporation Filed Feb. 23, 1954, Ser. No. 411,675

6 Claims. (Cl. 23204) oxide by effecting an exchange of deuterium between water and hydrogen sulfide as a gas, but a study of this procedure indicates that it has little or no advantage over other known methods. Comparatively small quantities of heavy water have also been produced by electrolysis, but the production thereof by these methods is not sufficient to supply the demand. Furthermore, it is not economical to operate an electrolysis plant for such a special purpose.

Since the vapor pressures of D 0, HDO and H differ slightly, it is possible to produce heavy water by distillation of normal water. However, one ton of normal water contains only about 150 grams of D 0 and the production of D 0 by a single distillation is only a few percent of the D 0 content. It is obvious, therefore, that such a process is'only practical in places where heat for the distillationeosts practically nothing. I

One of the objects of my invention is to provide a method which can be exercised in a relatively small, inconspicuous plant which can be built almost anywhere. Another object is to provide .a method in which the energy needed to effect the exchange is-comparatively small and hence the cost of operation is small as compared with any of the other methods used at the present time.

In order economically-to manufacture heavy water, the process should be one of isotope exchange because,

theoretically, such an exchange requires little or no energy. In actual practice however, energy must be expended for agitation, pumping, phases into the intimate contact necessary for the rapid establishment of equilibrium. Continuous counterflowing of the two phases is adapted to effect the desired exchange and thus provides the number of equilibrium stages necessary for eflicient isotope separation.

In order to maintain the cost at a minimum, the substances used should be inexpensive; there should be a rapid rate of exchange of the hydrogen; the separation factor should be large and, therefore, should have a considerable temperature coeflicient; the total volume of the system should be small which precludes the use of substances in gaseous form; extremes in temperature. should be avoided; the exchangeable hydrogen should constitute a large portion of theatoms of the molecules usedcin the system; and the two substances must be slightly miscible, but not toomiscible. a

I have discovered that water and hydrogen sulfide'fulfill practically "all of these conditions and I. propose to use these substances in the manner described below and illustrated in theaccompanyingdrawings in which- Fig. 1 is a schematic diagram of a first stageshowing the various elements necessary to effect an initial. deuterium enrichment of ordinary water;

Fig. 2 is a schematic diagram of another following etc., in order to bring item and effect counterflowing currents of the two phases stage similar to Fig. l but embodying certain modifications;

Fig. 3 is a diagrammatic illustration showing how the water may be progressively enriched by passing it through three separate stages to produce substantially pure D 0;

Fig. 4 is a schematic diagram showing the first stage of an alternate procedure; and

Fig. 5 is a schematic diagram showing another stage following that shown in Fig. 4.

In the drawings, the water phase is illustrated by heavy black lines and the hydrogen sulfide phase by two parallel lines.

Referring first to Fig. l, 1 and 2 represent confined zones such, for example, as towers through which counterflowing streams of water and hydrogen sulfide in liquid condition are forced to bring them into intimate, intermingling contact with each other; it being understood that the hydrogen sulfide is first compressed and cooled to change it from a gas to a liquid. As pointed out above, in order to effect an efficient hydrogen exchange, there should be a considerable temperature differential in the two zones. Merely for purposes of discussion, it will be assumed that zone 1 is maintained at a temperature of +40 C., while zone 2 is maintained at a temperature of 40 C. The system must be maintained under pressure sufficient to hold the hydrogen sulfide in liquid condition when at the higher temperature, and some substance, such as calcium chloride, must be added to the water in order tolower its freezing or solidifying point when at the lower temperature. Since the heating capacity of the water is small as compared to that of the hydrogen sulfide, it is advantageous to increase it by the addition of some inert solvent, such as alcohol, until the heat capacities of the two sreams are approximately equal.

In order to maintain the necessary pressure in the systhrough the zones 1 and 2, pumps 3 and 4 are introduced into water phase lines 5 and 6, and ptunps 7 and 8 are introduced in the pipe lines 9 and 10 carrying the hydrogen sulfide phase.

A transfer of deuterium from the hydrogen sulfide to the water takes place in the cold zone 2, While a transfer of deuterium from the water to the hydrogen sulfide takes place in the warm zone 1. Since the primary object is to effect a deuterium enrichment of the water, the pumps 7 and8 are of substantially greater capacity than the pumps 3 and 4, so that the volume of the hydrogen sulfide phase in the system is several times that of the water phase. For example, the hydrogen sulfide phase may be circulated at the rate of 1000 gallons per minute, while the water is circulated only at the rate of 200 gallons per minute.

The tcirculationand recirculation of the two phases results in a high concentration of deuterium oxide in the steam 5 flowing from the low temperature zone 2 and a high concentration of deuterium sulfide in the steam 10 flowing out of the zone of high temperature. Concurrently, the hydrogen sulfide in the stream 9 flowing out of the zone 2 of low temperature and the water in the stream 6 flowing out of zone 1 of high temperature will contain relatively low concentrations of deuterium sulfide and deuterium oxide, respectively.

Since the stream 5 flowing out of the zone 2 is at low temperature and must be heated before it passes into zone 1, and the stream 6 flowing out of zone 1 must be cooled before it enters zone 2, a heat exchange apparatus 11 is employed to elfect a transfer of heat from the stream 6 to the stream 5. Similarly, a heat exchange apparatus 12 is employed to effect a transfer of heat fiom the warm stream 10 flowing out of zone 1 to the cold stream 9 flowing out of zone 2.. As illustrated, heat exchanges are effected between two portions of the water phase and between two portions of the hydrogen sulfide phase, but it is to be understood that the exchanges may be effected between portions of the water phase and portions of the hydrogen sulfide phase which will be more eflicient than that illustrated if the heat capacities of the two phases are made approximately equal in the manner pointed out above.

Since the low temperature streams acquire heat from the surroundings, heat extraction or refrigeration units 13 and 14 are provided for cooling the Water phase and the hydrogen sulfide phase streams before they enter the ,cold zone 2, and heating units 15 and 16 are provided for heating the water and hydrogen sulfide phase streams, respectively, before they enter the warm zone 1.

The circulation of the streams as aforesaid will increase the concentration of D in the water phase from 1 part in 7000 to about 1 part in 70 before a steady state is reached.

A small stream 17 of the enriched water phase may then be withdrawn from the line at the point 18 to an electrolytic enrichment unit 19 and the stripped Water phase returned through line 20 and pump 21 to an appropriate point 22 in the first stage.

In order to compensate for the deuterium removed from the system in the stream 17, deuterium is added by withdrawing a small stream 23 from the hydrogen sulfide phase at a point, such as 24, where it is depleted in deuterium, and passed through an exchange zone 25 through which a counterflowing stream of deaerated water is forced by the pump 26. The zone 25 is maintained at substantially the same temperature as the zone 1. Thus, the depleted hydrogen sulfide phase acquires deuterium from the water and flows back as stream 27 into an appropriate point 28 in the main system. The water leaving the zone 25 in stream 29 flows into the separating unit 30, the hydrogen sulfide contained therein is recovered, compressed and cooled to a liquid condition in apparatus 31 and returned to the depleted hydrogen sulfide phase in the main system at the point 32. The water, free from the hydrogen sulfide and part of its deuterium content may be discharged as waste through the drain 33.

Further enrichment of the water may be accomplished by utilizing additional stages of the two-temperature process described above to produce a predetermined concentration of deuterium oxide in the final effluent stream. Thus, referring to Fig. 2, the small stream 17 withdrawn from the stage shown in Fig. 1 may be further enriched by delivering it to a warm zone 1 of another stage of the system. Concentration .to the desired level is eifected by circulation through the zones 1' and 2' thereof operating at high and low temperatures, respectively. Heat exchange units 34- and 35, similar to the heat exchange units 11 and 12, are provided and additional heating units 36 and 37, similar to the units 15 and 16, and refrigerating units 38 and 39, similar to the units 13 and 14, are also provided. Although no pumps are shown in Fig. 2 similar to the pumps 3, 4, 7 and 8 of Fig. 1, it is to be understood that such pumps are provided in the stage shown in Fig. 2. Since smaller volumes are processed in this and any following stages, the zones 1' and 2 and the various units mentioned may be smaller than the corresponding zones and units in the preceding stage.

Prior to employing the electrolytic enrichment scheme, the concentrated water phase may form the feed to still another stage and the processing repeated until the desired enrichment is achieved. However, prior to employing the electrolytic enriching scheme, it will be necessary to remove the calcium chloride or other freezing point depressant, and the dissolved hydrogen sulfide, from the enriched water phase. This may be accomplished in a distillation desorption apparatus 40' from which hydrogen sulfide in the form of gas is removed, cooled, compressed and returned through the line 41 to the main system at an appropriate point 42. Another at point 57'.

4 water phase stream 43 wherein the calcium chloride or other freezing point depressant is highly concentrated can be returned to an appropriate point 44 in the main system, while the enriched water phase is delivered to the device 45 where a final concentration of deuterium in the water may be eifected by electrolysis.

Fig. 3 is a detailed diagram of the electrolytic device 45 which may comprise several units, 46, 47 and 48, such 'as shown in Fig. 3. Thus, the enriched Water from which the hydrogen sulfide and the calcium chloride or other freezing depressant have been separated is introduced through the pipe 49. Further enrichment depends on the fact that the ratio of heavy hydrogen to normal hydrogen evolved as gases from the electrolytic units is less than the corresponding ratio in the residual liquid. As a result, in passing through a sufficient number of units in the manner indicated, a liquid stream 50 of substantially pure deuterium oxide may be obtained as a final product. Gaseous hydrogen and deuterium evolved from the units 46, 47 and 48 are converted to their oxides in the reactors 51, 52 and 53, respectively. Ordinary air or oxygen-enriched air may be used to combine with the gaseous deuterium hydrogen stream in the reactors. Condensed and cooled products of the reactions consisting of a mixture of normal and heavy Water are returned to the preceding electrolytic cell in each case as indicated, except for the stream 54 flowing from the first unit 46 which is returned to an appropriate point 55 in the main system.

An alternate method of carrying out the enrichment is shown in Figs. 4 and 5, wherein 1 and 2 and 1' and 2' are the high and low temperature zones in said figures respectively. In Fig. 4 pumps 3, 4, 7 and 8; the heat exchange units 11 and 12; the refrigerating units 13 and 14; and the heating units 15 and 16; are the same as in Fig. 1.

Here, instead of using the water phase as the source of deuterium to the enriching units, the liquid hydrogen sulfide stream is used. This is taken from the first stage of enrichment at a point 56 as a portion of the stream 10, and forms the feed to the next stage 57 of the enriching apparatus, shown more in detail in Fig. 5.

To compensate for the loss in deuterium due to that withdrawn from point 56 With the liquid containing the enriched hydrogen sulfide, the same procedure as that described in connection with Fig. 1 is followed. Thus, liquid containing depleted hydrogen sulfide is withdrawn through pipe 23 from an appropriate point 24, run through the exchange zone 25, at the temperature of the zone 1, in a direction counter to that of a stream of deaerated Water from the pump 26, Where it is enriched, and returned through pipe 27 to the main stage at an appropriate point 28. Liquid containing the deuterium depleted Water and some hydrogen sulfide is delivered through pipe 29' to unit 30 wherein the hydrogen sulfide is separated from the water, cooled and compressed to liquid form in unit 31, and returned to the main stage at an appropriate point 32.

The next stage, represented by 57 in Fig. 4, is shown in detail in Fig. 5. Here, the zones 1' and 2; the heat exchange units; the refrigerating units; and the heating units may be the same as shown in Fig. 2 and are indicated by the same numerals. As mentioned above in connection with Fig. 2, the volumes of the zones 1 and 2 may be much smaller than those of the first stages shown in Figures 1 and 4. No circulating pumps are shown in Fig. 5 but it is to be understood that such pumps are used although they may he of smaller capacity than the first stage pumps.

The liquid containing the enriched hydrogen sulfide which is withdrawn from the previous stage at point 56 (see Fig. 4) is delivered to the next stage shown in Fig. 5 The hydrogen sulfide phase is circulated through pipe line 10, heat exchange unit 35, refrigerating unit 39, heating unit 37, and through the zones 1 and 2 in a direction counter to that of the water phase which is circulated through heat exchange unit 34, heating unit 36, refrigerating unit 38, and through the zones 1' and 2.

Liquid containing deuterium enriched water is withdrawn from this stage at an appropriate point 58 and passed through the distillation desorption apparatus 40, similar to that described in connection with Fig. 2, wherein the hydrogen sulfide is separated from the water, cooled and compressed to liquid form and returned to the main system through pipe 41 at point 42, as in Fig. 2.

Another water phase stream 43 wherein the calcium chloride or other freezing point depressant is highly concentrated is returned to an appropriate point 44 in the main system, while the enriched water phase may be delivered to the apparatus 45 for final concentration of the deuterium in the water by electrolysis. The apparatus 45 may comprise several units as described in connection with Fig. 3. The deuterium depleted water from 45 is returned through pipe 54 to an appropriate point 55 in the main system, as in Fig. 2.

The loss in deuterium in the main system may be compensated by withdrawing a part of the depleted hydrogen phase from the point 58 and delivering it to an enriching zone like that shown at 25 in Figs. 1 and 4.

If desired, the hydrogen sulfide phase may be further enriched in another stage by withdrawing part thereof from an appropriate point such as 60.

While I have described my invention in its preferred embodiment, it is to be understood that the words which I have used are words of description rather than of limitation and that changes, within the purview of the appended claims, may be made without departing from the true scope and spirit of my invention in its broader aspects.

What I claim is:

1. Those steps in the making of heavy water which comprise effecting a first deuterium enrichment of water by producing circulating, counterfiowing, intermingling streams of said water containing an agent which has reduced the freezing point thereof to a temperature substantially below 0 C., and hydrogen sulfide in a liquid condition through two separate zones at substantially different temperatures, one of which is below 0 C.; withdrawing liquid containing enriched water from the circulating mass and compensating for the reduction in the deuterium content of said circulating mass due to the withdrawing of said enriched water, by withdrawing liquid containing hydrogen sulfide from said mass at a point where it has a comparatively low deuterium content; eifecting a deuterium enrichment of said withdrawn hydrogen sulfide by circulating and intermingling it with a counterflowing stream of water in a third separate zone at a temperature of the order of that one of the first mentioned zones which is the higher; and returning it to said zone of higher temperature.

2. The method set forth in claim 1 in which the temperature in the zone of lower temperature is maintained at a point substantially below 0 C., and the temperatures 6 in the other zones are maintained at points substantially above 0 C.

3. The method set forth in claim 1 in which the temperature diiferential of said zones is of the order of about C.

4. Those steps in the method of manufacturing heavy water which comprise compressing and cooling hydrogen sulfide until it is in a liquid state; producing circulating, counterflowing, intermingling streams of said hydrogen sulfide and water containing an agent which has reduced the freezing point of said water to a temperature substantially below 0 C., through two separate zones at substantially difierent temperatures, one of which is below 0 C., while maintaining pressure-temperature relations in said zones which will maintain both streams in liquid condition; subjecting each of said streams to heat after it flows from the zone of lower temperature and before it enters the zone of higher temperature, and to a refrigerating treatment after its leaves the zone of higher temperature and before it enters the zone of lower temperature; whereby a transfer of deuterium from said hydrogen sulfide to said water will be effected in said zone of lower temperature, and a transfer of deuterium from said water to said hydrogen sulfide will be effected in said zone of higher temperature; withdrawing liquid containing deuterium enriched water from said circulating mass at a point where said water has attained its maximum degree of enrichment; and replenishing the supply of deuterium in the hydrogen sulfide circulating through said zones by withdrawing from said circulating mass some of the liquid containing deuterium-depleted hydrogen sulfide and effecting a transfer of deuterium thereto by flowing it intermingled with a counter-flowing stream of water in a third zone at said higher temperature, and feeding it back into the liquids circulating through said first mentioned zones at a point where the circulating streams are at the higher temperature.

5. The steps set forth in claim 4 in which the temperature in the zone of lower temperature is maintained at a point substantially below 0 C., and the temperatures in the other zones are maintained at points substantially above 0 C.

6. The steps set forth in claim 4 in which the temperature tgfferential of said zones is of the order of about 100 References Cited in the file of this patent UNITED STATES PATENTS 2,690,380 Taylor Sept. 28, 1954 2,741,543 Urey Apr. 10, 1956 2,787,526 Spevack Apr. 2, 1957 OTHER REFERENCES Babor and Lehrman, General College Chemistry, 2nd ed., 1940, Thomas I. Crowell Co., New York, pp. 236- 283.

Chemical Abstracts, vol. 22 (1928), p. 3083; vol. 45 (1951), p. 10009e, vol. 31, p. 4877. 

1. THOSE STEPS IN THE MAKING OF HEAVY WATER WHICH COMPRISE EFFECTING A FIRST DEUTERIUM ENRICHMENT OF WATER BY PRODUCING CIRCULATING, COUNTERFLOWING, INTERMINGLING STREAMS OF SAID WATER CONTAINING AN AGENT WHICH HAS REDUCED THE FREEZING POINT THEREOF TO A TEMPERATURE SUBSTANTIALLY BELOW 0*C., AND HYDROGEN SULFIDE IN A LIQUID CONDITION THROUGH TWO SEPARATE ZONES AT SUBSTANTIALLY DIFFERENT TEMPERATURES ONE OF WHICH IS BELOW 0*C., WITHDRAWING LIQUID CONTAINING ENRICHED WATER FROM THE CIRCULATING MASS AND COMPENSATING FOR THE REDUCTION IN THE DEUTERIUM CONTENT OF SAID CIRCULATING MASS DUE TO THE WITHDRAWING OF SAID ENRICHED WATER, BY WITHDRAWING LIQUID CONTAINING HYDROGEN SULFIDE FROM SAID MASS AT A POINT WHERE IT HAS A COMPARATIVELY LOW DEUTERIUM CONTENT, EFFECTING A DEUTERIUM ENRICHMENT OF SAID WITHDRAWN HYDROGEN SULFIDE BY CIRCULATING AND INTERMINGLING IT WITH A COUNTERFLOWING STREAM OF WATER IN A THIRD SEPARATE ZONE AT TEMPERATURE OF THE ORDER OF THAT ONE OF THE FIRST MENTIONED ZONES WHICH IS THE HIGHER, AND RETURNING IT TO SAID ZONE OF HIGHER TEMPERATURE. 